JP2007277114A - Adhesive composition for dental restored material made form ceramics - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a dental resin used for bonding with a dental restoration material made from ceramics, having a high bonding property for capable of eliminating a primer treatment, and capable of preserving the reagent stably even in a preservation form oftained by mixing the constituting components as one agent and excellent in the operability of the preparation of the reagent on its use. <P>SOLUTION: This adhesive composition for the dental restoration material made from the ceramics consists of a preservation form obtained by mixing at least each of the following (A) to (E) as one agent: (A) a radically polymerizable monomer; (B) a coupling agent, suitable a silane-coupling agent having a polymerizable group; (C) a photosensitive pigment; (D) a photo acid-forming agent and/or photo base-forming agent; and (E) a photoradical-generator. Alternatively, in the case of using the photo acid-forming agent as the above component (D), each of components of an aryl borate compound or a sulfinic acid salt and further desirably (F) a filler are incorporated. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an adhesive composition for a dental restoration made of ceramics, and more specifically, relates to the adhesive composition for a dental restoration made of ceramics comprising a storage form in which each component such as one paste type is mixed in one agent. .

  In dentistry, ceramic restorations such as crowns and inlays are bonded to the tooth with a dental resin such as resin cement for the purpose of repairing carious or missing teeth. Here, the dental resin contains a radically polymerizable monomer as a curable component, and after being applied to a ceramic dental restoration, the applied surface is brought into contact with a treatment site of a tooth in the oral cavity. These are used after being cured by photopolymerization or the like.

  However, the familiarity between the ceramic material, which is an inorganic material, and the polymer of the radical polymerizable monomer is poor, and the adhesive strength between the ceramic dental restoration and the dental resin was not satisfactory. Therefore, in order to improve this adhesive strength, the ceramic dental restoration is subjected to surface treatment in advance with a surface treatment agent (ceramic primer) mainly composed of a silane coupling agent.

  Thus, the specific composition of the primer for ceramics is, for example, an organic solution containing an organometallic compound such as zinc 2-ethylhexanoate and dibutyltin dilaurate as a reaction catalyst together with the silane coupling agent. Things are known. In addition to the silane coupling agent, a compound containing an acidic organic phosphorus compound having at least one olefinic double bond capable of radical polymerization in the molecule has been proposed (Patent Document 1). In this latter primer, the acidic organophosphorus compound acts as a catalyst that activates the silane coupling agent and promotes condensation of silanol groups on the ceramic surface.

  If the ceramic primer is used, the adhesive strength between the dental restoration made of ceramic and the dental resin will be excellent, but such pretreatment is also complicated in operation, and if not possible, In a dental resin, it has been desired to further increase the adhesive strength.

  Against this background, the structure of the above-mentioned primer for ceramics is applied to a dental resin, and an acidic organic phosphorus compound having an olefinic double bond capable of radical polymerization is used as a part of the radical polymerizable monomer. And the adhesive composition which mix | blended the silane coupling agent is proposed and it is reported that favorable adhesive strength is obtained (patent document 2).

JP 63-51308 A JP-A-7-277913

  However, in the case of an adhesive composition using a combination of such an acidic organophosphorus compound and a silane coupling agent, when the reagent composition is a mixture of these, the silane coupling agent is stored during storage. Since a condensation reaction occurred, the reagent had to be stored in two parts. Therefore, it is necessary to mix the two members immediately before use, and the adhesive composition still has room for improvement in terms of the complexity of the mixing operation.

  With the above background, the present invention is a dental resin used by adhering to a dental restoration made of ceramics, and has a high adhesive property that can eliminate the primer treatment, and the components are mixed and stored. It is an object of the present invention to develop a reagent that can store a reagent stably even in the form and has excellent operability of reagent adjustment at the time of use.

  The present inventors have intensively studied to overcome the above problems. As a result, if the composition of the adhesive composition using a radical polymerizable monomer is combined with a coupling agent, a sensitizing dye, a photoacid generator and / or a photobase generator, the reagent During storage, the acid or base is not present in the system and is stable.On the other hand, in use, when the light is irradiated to polymerize the radical polymerizable monomer, the sensitizing dye, and A photoacid generator or a photobase generator acts to generate an acid or a base, which activates the coupling agent, resulting in high strength between the cured product of the adhesive composition and the ceramic dental restoration. As a result, the present invention was completed.

That is, the present invention has at least the following (A) to (E).
(A) a radical polymerizable monomer,
(B) Coupling agent (C) Sensitizing dye (D) Photoacid generator and / or photobase generator, and (E) Photoradical generator, or a photoacid generator as the component (D) was used. In some cases, it is an adhesive composition for dental restorations made of ceramics having a storage form in which each component of an aryl borate compound or sulfinate is mixed in one agent.

  The adhesive composition of the present invention has excellent adhesiveness to ceramic dental restorations, and the adhesive strength is high enough to eliminate the pre-priming. Furthermore, although each component is mixed in one agent, the coupling agent is stable, the high adhesive strength can be maintained well for a long period of time, and it can be used with high reliability. Therefore, the present invention that provides such an adhesive composition capable of stably exhibiting such a high adhesive strength for a long period of time in a one-part storage form without any reagent mixing operation immediately before use is extremely useful.

  In the adhesive composition of the present invention, when applied to a dental restoration made of ceramics and irradiated with light, in parallel with the polymerization of the radical polymerizable monomer, a photoacid generator by a sensitizing dye or A decomposition reaction of the photobase generator also occurs to generate an acid and / or a base. The generated acid or base activates the coupling agent and reacts well with the ceramic dental restoration. As a result, the cured product of the adhesive composition is firmly bonded to the restoration by the action of the coupling agent that has reacted to the surface of the ceramic dental restoration.

  In addition, when an acid is generated by light irradiation using a sensitizing dye and a photoacid generator, when an aryl borate compound or a sulfinate is added to the adhesive composition of the present invention, Since this compound reacts with an acid to generate radicals, the radically polymerizable monomer can be polymerized with good polymerization activity without using a photoradical generator. is there.

  Further, according to the adhesive composition of the present invention having such a configuration, even if each component is mixed and stored in one agent, the acid or the acid that activates the coupling agent until light is irradiated. The base is not present in the system. Therefore, it is possible to store the reagent stably for a long period of time, and during use, no mixing operation is required, and the reagent can be used as it is and has excellent operability.

  In the adhesive composition of the present invention, the (A) radical polymerizable monomer is not particularly limited, and a known monofunctional or polyfunctional radical polymerizable monomer can be used.

  In the radical polymerizable monomer, examples of the group having an unsaturated bond capable of radical polymerization include a methacryloyloxy group, an acryloyloxy group, a methacrylamide group, an acrylamide group, a styryl group, and an allyl group. Among these, a (meth) acrylate polymerizable monomer having a methacryloyloxy group or an acryloyloxy group is preferable in terms of polymerizability, adhesiveness, and ease of handling.

  Specific examples of monofunctional radically polymerizable monomers that are preferably used generally include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl. (Meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Monofunctional (meth) acrylate monomers such as hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate and methoxydiethylene glycol (meth) acrylate: monofunctional (meth) acrylic such as N-methylol (meth) acrylamide De monomers: styrene, monofunctional styrenic monomers such α- methyl styrene.

  Specific examples of polyfunctional radically polymerizable monomers that are preferably used in general are 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane, 2,2 '-Bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meta ) Acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxyethoxyphenyl) 2- (4- (meth) acryloyloxydiethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- ( 4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, 1- ( Aromatic bifunctional (meth) acrylate monomers such as (meth) acryloyloxymethyl-2- (meth) acryloyloxyethyl hydrogenmalate: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acryl , Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, di-2- (meth) acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate, N, N′-methylenebis Aliphatic bifunctional (meth) acrylate monomers such as (meth) acrylamide: Bifunctional (meth) acrylic acid amide monomers such as N, N′-methylene (bis) acrylamide: divinylbenzene, α-methyl Bifunctional styrene monomer such as styrene dimer: diallylphthale Bifunctional allylic monomers such as silicate, diallyl phthalate, and diallyl carbonate: Trifunctional (meth) acrylate monomers such as trimethylolpropane tri (meth) acrylate and trimethylolethane tri (meth) acrylate: pentaerythritol And tetrafunctional (meth) acrylate monomers such as tetra (meth) acrylate.

  The above radical polymerizable monomers may be used alone or in combination of two or more.

  As the (B) coupling agent used in the adhesive composition of the present invention, known coupling agents can be used without limitation. Here, the coupling agent is a surface treatment agent capable of chemically bonding an organic material and an inorganic material, and is composed of a compound having an organic functional group and a hydrolyzable group in the molecule.

  Such coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ -(Meth) acryloyloxypropyltris (β-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltri (trimethylsiloxy) silane, ω- (meth) acryloyloxydecyltrimethoxysilane, γ- (meth) acryloyloxy Propylpentamethyldisiloxane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, Silane coupling agents such as mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, hexamethyldisilazane, isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropylisostearoyldi Acrylic titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tricumyl phenyl titanate, etc. Titanate coupling agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate and the like.

  Among these coupling agents, a silane coupling agent having a polymerizable group is particularly preferably used from the viewpoints of adhesiveness and handleability. Here, examples of the polymer group include a vinyl group, a (meth) acryloyloxy group, and an allyl group, and a (meth) acryloyloxy group is particularly preferable from the viewpoint of adhesiveness.

  Specific examples of the silane coupling agent having a polymer group that is suitably used include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane, ω-methacryloxydecyltrimethoxysilane, γ-methacryloxypropyl pentamethyldisiloxane can be mentioned.

  Said coupling agent can also be used 1 type or in combination of 2 or more types.

  In the adhesive composition of the present invention, the concentration of such a coupling agent is not particularly limited, but from the viewpoint of adhesive strength, it is within the range of 0.01 to 25 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer. Preferably it is. A more preferable concentration range of the coupling agent concentration is 0.05 to 12 parts by weight.

  The sensitizing dye (C) used in the adhesive composition of the present invention has a maximum absorption wavelength of 350 to 680 nm and can be decomposed by exciting a polymerization initiator that does not absorb visible light by energy transfer. It is a dye, and in the present invention, it is a dye capable of generating an acid and a base by sensitizing and decomposing the photoacid generator and the photobase generator as component (D).

  As this sensitizing dye, a sensitizing dye having a maximum absorption wavelength of 350 to 680 nm can be used without any limitation. Examples of sensitizing dyes that can be suitably used include coumarin dyes, cyanine dyes, merocyanine dyes, thiazine dyes, azine dyes, acridine dyes, xanthene dyes, squalium dyes, and pyrilinium salt dyes. It is done. Of these, coumarin dyes and cyanine dyes are preferred because (D) photoacid generators and photobase generators described later can be efficiently sensitized and decomposed.

  Specific examples of coumarin dyes include 3-thienoyl coumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoylcoumarin, 3- (4-cyanobenzoyl) coumarin, 3-thienoyl-7-methoxycoumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-methoxycoumarin, 3- (4-cyanobenzoyl) -7-methoxycoumarin, 5,7-dimethoxy-3- (4-methoxybenzoyl) ) Coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- (4-cyanobenzoyl) -5,7-dimethoxycoumarin, 3-acetyl-7-dimethylaminocoumarin, 7-diethylamino-3-thienoylcoumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 3-benzoyl 7-diethylaminocoumarin, 7-diethylamino-3- (4-cyanobenzoyl) coumarin, 7-diethylamino-3- (4-dimethylaminobenzoyl) coumarin, 3-cinnamoyl-7-diethylaminocoumarin, 3- (p-diethylaminocinna) Moyl) -7-diethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-carboxy-7-diethylaminocoumarin, 3- (4-carboxybenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbiscoumarin, 3 , 3′-carbonylbis (7-diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-10- (benzothiazoyl) -11-oxo-1H, 5H, 11H,-[1] benzopyrano [6,7,8-ij Quinolidine, 3,3′-carbonylbis (5,7-) dimethoxy-3,3′-biscoumarin, 3- (2′-benzimidazolyl) -7-diethylaminocoumarin, 3- (2′-benzoxazoyl) ) -7-diethylaminocoumarin, 3- (5′-phenylthiadiazoyl) -7-diethylaminocoumarin, 3- (2′-benzthiazoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (4-cyano-) 7-diethylamino) coumarin, 4-trifluoromethyl-7-aminocoumarin, 4-trifluoroethyl-7-dimethylaminocoumarin, 3-phenyl-7-aminocoumarin, 3- (4′-acetylaminophenyl) -7 -Acetylaminocoumarin, 3-phenyl-7- (2H-naphtho [1,2d] triazol-2'-yl) c Marine, 3-ethoxycarbonyl-5,6-benzocoumarin, 4-trifluoromethylpiperidino [3,2-g] coumarin, 3- (2′-benzothiazoyl) -4-cyano-7-diethylaminocoumarin Etc.

  Examples of cyanine dyes include 3,3′-diethyl-2,2′-thiocyanine iodide, 1,3,3,1 ′, 3 ′, 3 ′,-hexamethyl-2,2′-indocyanine perchlorate. 1,3′-diethyl-2,2′-quino-thiacyanine iodide, 1,3′-diethyl-2,2′-quino-selenocyanine iodide, 1,1′-diethyl-2,2 ′ -Monomethine cyanine dyes such as quinocyanine iodide, 1,1'-diethyl-2,4'-quinocyanine iodide, 1,1'-diethyl-4,4'-quinocyanine iodide: 3,3 ' -Diethyl-2,2'-thiazolinocarbocyanine iodide, 3,3'-diethyl-2,2'-thiazolinocarbocyanine iodide, 3,3'-diethyl-2,2'-oxacarbosi Nine iodide, 3,3 ′, 9-triethyl-5,5′-diphenyl-2,2′-oxacarbocyanine iodide, 1,3,3,1 ′, 3 ′, 3′-hexamethyl-2,2 ′ -Thiacarbocyanine iodide, 3,3'-diethyl-2,2'-thiacarbocyanine iodide, 3,3 ', 9-triethyl-2,2'-(6,7,6 ', 7'- Trimethine cyanine dyes such as dibenzo) thiacarbocyanine iodide and 1,1′-diethyl-2,4′-quinocarbocyanine iodide: 3,3′-diethyl-2,2′-oxadicarbocyanine iodide 3,3′-diethyl-9,11-neopentylene-2,2′-thiadicarbocyanine iodide, 3,3′-diethyl-2,2′-selenadicarbocyanine iodide Pentamethinecyanine cyanine dyes such as and the like.

  Other suitable specific examples of merocyanine dyes include 3-ethyl-5- [2- (3-methyl-2-thiazolidinylidene) ethylidene] -2-thio-2,4-oxazolidinedione, 1 , 3-Diethyl-5- [2- (3-ethyl-2-benzothiazolinylidene) ethylidene] -2-thiohydantoin, 3-carboxymethyl-5- [2- (3-ethyl-2-benzothia Zolidinylidene) ethylidene] rhodanine, 3-ethyl-5- [2- (3-ethyl-2-benzothiazolinylidene) ethylidene] rhodanine, 3-ethyl-5- [2- (3-ethyl-4- Methyl-2-thiazolinylidene) ethylidene] rhodanine and the like.

  Specific examples of thiazine dyes include methylene blue and 3,7-diamino-1,2-benzophenoxazonium perchlorate. Examples of azine dyes include 5-acetoxybenzophenazine, 1- Examples include amino-4-nitrophenazine.

  Furthermore, specific examples of acridine dyes include 1-aminoacridine, 9- (2'-hydroxystyryl) acridine, acridine orange and the like.

  Furthermore, specific examples of xanthene dyes include rhodamine 110, rhodamine 6G, tetramethylrhodamine perchlorate, and specific examples of squalium dyes include 2-[[3-[(1, 3-Dihydro-1-ethyl-3,3,5-trimethyl-2H-indole-2-ylidene) methyl] -2-hydroxy-4-oxo-2-cyclobuten-1-ylidene] methyl] -1-ethyl- 3,3,5-trimethyl-3H-indolium, inner salt, {4- [3- [4- (N, N-diethylamino) -2-hydroxyphenyl] -2-hydroxy-4-oxo-2-cyclobutene -1-ylidene] -3-hydroxy-2,5-cyclohexadiene-1-ylidene} -N-ethyl-N-octadecylammonium hydroxide It includes internal salts.

  Furthermore, preferable specific examples of the pyrilinium salt dye include 2,6-diphenyl-4- (4-methylphenyl) thiopyrririnium perchlorate and 2,6-bis (4-methylphenyl) -4- (4. -Phenyl) thiopyrilinium perchlorate, 2,4,6-triphenylthiopyrilinium perchlorate and the like.

The sensitizing dye to be used may be appropriately selected and used depending on the wavelength and intensity of light used for the polymerization or the type and amount of the photoacid generator and photobase generator indicated by the component (D). It can be used by mixing more than one species. The amount of these sensitizing dyes is not particularly limited as long as the effect is exhibited, but is preferably 5 × 10 ⁻⁷ to 10 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer, The blending of 5 × 10 ^{−6 to} 5 parts by weight is more preferable. Further, the mixing ratio of the sensitizing dye to the photoacid generator and the photobase generator also varies depending on the types of other components to be combined, but usually the sensitizing dye and the photoacid generator and / or the photobase generator Is selected from the range of 0.01 to 80% by mass, more preferably 0.05 to 60% by mass.

  The photoacid generator (D) used in the adhesive composition of the present invention generates Bronsted acid or Lewis acid by light irradiation, and is visible by the sensitizing dye represented by the component (C) of the present invention. As long as it decomposes under irradiation with light and generates an acid, a known one can be used without any limitation.

  Examples of this photoacid generator include halomethyl group-substituted s-triazine derivatives, diphenyliodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, disulfone compounds, diazonium salt compounds and the like.

  In the present invention, among the above photoacid generators, in particular, when a halomethyl group-substituted s-triazine derivative photoacid generator or a diphenyliodonium salt photoacid generator is used, sensitization shown by component (C) It is suitable because it transfers energy with the dye and generates acid with high efficiency by irradiation with visible light.

  A typical halomethyl group-substituted s-triazine derivative is represented by the following general formula (1).

(Wherein, R ¹ and R ² are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkoxy group, R ¹ and R ² A halomethyl group-substituted s-triazine derivative represented by the following formula:

  Furthermore, when a typical diphenyliodonium salt compound is represented by a general formula, the following general formula (2)

(However, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkenyl group and alkoxy group, respectively, and M ⁻ is a halogen ion, BF _{^{4 -, PF 6 -, AsF}} 5 -, CF 3 SO 3 - and SbF ₆ ^-. a a) diphenyliodonium salt compound represented by the like.

  The halogen atom substituted for the halomethyl group in the general formula (1) is preferably a halogen atom of chlorine, bromine or iodine, but a compound having a trichloromethyl group in which three chlorine atoms are substituted is used. It is common.

  Hereinafter, specific examples of halomethyl group-substituted s-triazine derivatives include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (o-methoxystyryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -4,6-bis Trichloromethyl) -s-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine and the like can be mentioned.

  Specific examples of the diphenyliodonium salt compound represented by the general formula (2) are diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (m -Nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, chlorides such as p-octyloxyphenylphenyliodonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimony And trifluoromethanesulfonate, and tetrafluoroborate, hexafluorophosphate, hexafluoroarcetate in particular from the viewpoint of the solubility of the compound. Over DOO, hexafluoroantimonate, is trifluoromethane sulfonate salt is preferably used.

  Specific examples of other photoacid generators preferably used in the present invention include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphinate, triphenylsulfonium hexafluoroantimonate as sulfonium salt compounds. , Triphenylsulfonium trifluoromethane sulfonate, p-methoxyphenyl diphenyl sulfonate hexafluoroantimonate, p-methoxyphenyl diphenyl sulfonate trifluoromethane sulfonate, p-toluene diphenyl sulfonate hexafluoroantimonate, p-toluene diphenyl sulfonate trifluoromethane sulfonate Mesitylene diphenyl sulfonate trifluoromethane sulfonate, p- (t-butyl) phenyl diphe Sulfonates trifluoromethane sulfonate, and the like.

  Specific examples of the sulfonic acid ester compound include benzoin tosylate, α-methylol benzoin tosylate, pyrogallol trimesylate, and the like.

  Furthermore, specific examples of the disulfone compound include diphenyldisulfone, di (p-tolyl) disulfone and the like, and specific examples of the diazonium salt compound include naphthoquinone (1,2) diazide (2) -4-sulfonate sodium. Naphthoquinone (1,2) diazide (2) -5-sulfonic acid sodium, naphthoquinone (1,2) diazide (2) -5-sulfonic acid tosyl ester, and the like.

  The above photoacid generators may be used alone or in combination of two or more. The amount of these photoacid generators is not particularly limited as long as the effect is exhibited, but is preferably 0.001 to 12 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer. More preferred is 0.005 to 6 parts by weight. Further, the blending ratio of the photoacid generator to the sensitizing dye also varies depending on the kinds of other components to be combined, but is usually 20 in the total amount of (C) sensitizing dye and (D) photoacid generator. It is selected from the range of ˜99.99 mass%, more preferably 40 to 99.95 mass%.

  On the other hand, the photobase generator used as component (D) generates Bronsted base or Lewis base by light irradiation, and decomposes under irradiation with visible light by the sensitizing dye represented by component (C) of the present invention. Any known base can be used without any limitation.

  Examples of the photobase generator include orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos, N-formylated aromatic aminos, N-acylated aromatics. Group aminos and the like.

  Among the photobase generators used in the present invention, in particular, when an orthonitrobenzyl carbamate photobase generator or an α, α-dimethyl-3,5-dimethoxybenzylcarbamate photobase generator is used, (C) It is suitable because it performs energy transfer with the sensitizing dye represented by the component and generates a base with high efficiency by irradiation with visible light.

  Orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy] carbonyl. ] Hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [[ (2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[( 2-Nitrobenzyl) oxy] carbo Ru] diaminodiphenylmethane, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] propylamine, [[(2,6-dinitrobenzyl) oxy ] Carbonyl] butylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] aniline, bis [[(2,6-dinitrobenzyl) oxy ] Carbonyl] ethylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] phenylenediamine, and the like.

  Examples of α, α-dimethyl-3,5-dimethoxybenzylcarbamate include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl-3. , 5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] butylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl). ) Oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl Aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperidine, [[(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] ethylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine, bis [ And [(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine.

  Acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl acetone oxime, acryloyl acetophenone oxime, alloyl benzophenone oxime, Examples include acroyl acetone oxime.

  Specific examples of N-formylated aromatic aminos and N-acylated aromatic aminos include, for example, di-N- (p-formylamino) diphenylmethane, di-N (p-aceethylamino) diphenylmelane, Di-N- (p-benzoamido) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetylaminonaphthalene, 1,5 -Diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5-diformylaminoanthraquinone, 3,3'- Dimethyl-4,4′-diformylaminobiphenyl, 4,4′- Such as formyl amino benzophenone.

  The above photobase generators may be used alone or in combination of two or more. The blending amount of these photobase generators is not particularly limited as long as the effect is exhibited, but is preferably 0.001 to 12 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer. More preferred is 0.005 to 6 parts by weight. Moreover, although the compounding ratio of the photobase generator to the sensitizing dye also varies depending on the types of other components to be combined, it is generally 20 to 20 in the total amount of (C) sensitizing dye and (D) photobase generator. It is selected from the range of 99.99% by mass, more preferably 40 to 99.95% by mass.

  In the adhesive composition of the present invention, in order to cure the above-described radically polymerizable monomer (A) and harden the composition, the polymerization is performed by light irradiation after coating on a ceramic dental restoration. It is necessary to generate an amount of radicals that can smoothly progress. As one of the methods for that purpose, (E) a photoradical generator is mix | blended in a composition.

  As the photoradical generator, known compounds can be used without limitation among compounds that are excited by light irradiation to generate radicals. Examples of such photo radical generators include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, 1,2-phenanthrenequinone, 1, Α-diketones such as 4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, thioxanthones such as 2,4-diethylthioxanthone, 2-benzyl-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2- Benzyl-diethylamino-1- (4-morpholinophenyl) -pro Α-aminoacetophenone such as non-1,2-benzyl-dimethylamino-1- (4-morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphos And acylphosphine oxide derivatives such as fin oxide.

  The compounding amount of these photo radical generators is not particularly limited as long as the effect is exhibited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer. More preferably, the amount is 1 to 5 parts by weight.

  Moreover, it is desirable to add a photopolymerization accelerator for the purpose of accelerating the polymerization reaction of the radical polymerizable monomer by the photoradical generator.

  As photopolymerization accelerators, N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N , N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethyl Aminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, -Dimethylaminostilpene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine , Triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N- And tertiary amines such as diethylaminoethyl methacrylate and 2,2 '-(n-butylimino) diethanol, and barbituric acids such as 5-butyl barbituric acid and 1-benzyl-5-phenylbarbituric acid. I can do it.

  The blending amount of these photopolymerization accelerators is not particularly limited as long as the effect is exhibited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer. More preferably, the amount is 1 to 5 parts by weight.

  In addition, as a method for generating radicals by light irradiation by a method different from the method for generating radicals using such a photoradical generator, there are the following methods. That is, in the case where a photoacid generator is used as the component (D), an aryl borate compound or a sulfinate is added.

  Since both aryl borate compounds and sulfinates are compounds that react with an acid to generate radicals, the composition of the present invention uses a photoacid generator as (D) together with the (C) sensitizing dye. When an acid is generated at the time of irradiation, the generated acid not only activates the (B) coupling agent, but also serves well for polymerization of the (A) radical polymerizable monomer.

  The (E) aryl borates used in the adhesive composition of the present invention, when combined with a photoacid generator and a sensitizing dye, generate radicals by light irradiation and polymerize the above radical polymerizable monomers. As long as it is possible, known ones can be used without any limitation.

  Aryl borates include tetraphenyl boron, tetra (p-fluorophenyl) boron, tetra (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenyl boron, Dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) phenylboron, monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, Monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3,5-bistrifluoromethyl) phenylboron (wherein the alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.) Salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts and the like.

  The above aryl borate compounds may be used alone or in combination of two or more. The blending amount is not particularly limited as long as the effect is exhibited. However, 0.001 to 12 parts by weight is preferable with respect to 100 parts by weight of the radical polymerizable monomer, and 0.005 to 6 parts by weight. Is more preferable. Further, the compounding ratio of the aryl borate compound to the sensitizing dye and the photoacid generator also varies depending on the types of other components to be combined, but usually 10 to 90 in the total amount of the sensitizing dye and the photoacid generator. It is selected from the range of mass%, more preferably from 20 to 80 mass%.

  On the other hand, the (E) sulfinate used in the present invention can be combined with a photoacid generator and a sensitizing dye to generate radicals by light irradiation and polymerize the above radical polymerizable monomer. Any known one can be used without any limitation.

  Examples of sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, lithium p-toluenesulfinate, potassium p-toluenesulfinate, sodium m-nitrobenzenesulfinate, p-fluorobenzenesulfinate Sodium etc. are mentioned.

  The above sulfinates may be used alone or in combination of two or more. The blending amount is not particularly limited as long as the effect is exhibited. However, 0.001 to 12 parts by weight is preferable with respect to 100 parts by weight of the radical polymerizable monomer, and 0.005 to 6 parts by weight. Is more preferable. Further, the blending ratio of the sulfinate to the sensitizing dye and the photoacid generator also varies depending on the types of other components to be combined, but usually 10 to 90 in the total amount of the sensitizing dye and the photoacid generator. It is selected from the range of mass%, more preferably from 20 to 80 mass%.

  Both the aryl borate compound and the sulfinate described above can be used in combination.

  It is preferable that the adhesive composition of the present invention further contains (F) filler from the viewpoint of improving the mechanical strength and water resistance of the cured product of the adhesive composition of the present invention. In addition, the (A) radical polymerizable monomer as exemplified above is usually in a liquid state at room temperature, and therefore the adhesive composition of the present invention is in a liquid state when mixed with each component. Usually, it is paste-like by blending the filler in this way, and its viscosity and fluidity can be adjusted. As this filler, known organic fillers and inorganic fillers can be used without limitation.

  Specific examples of organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane trimethacrylate copolymer, polychlorinated. Examples include vinyl, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

  Specific examples of the inorganic filler include quartz, amorphous silica, silica zirconia, fluoroaluminosilicate, clay, aluminum oxide, talc, mica, kaolin, glass, barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride, Examples thereof include titanium nitride, silicon carbide, boron carbide, calcium carbonate, hydroxyapatite, and calcium phosphate.

  Furthermore, it is desirable to treat these inorganic fillers with a surface treatment agent typified by a silane coupling agent in order to improve the compatibility with the polymerizable monomer and improve the mechanical strength and water resistance. The surface treatment may be carried out by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, hexamethyldisilazane or the like is preferably used.

  Inorganic organic composite fillers obtained by pulverizing a composite of an inorganic oxide and a polymer obtained by polymerizing and curing a radical polymerizable monomer mixture in which various inorganic fillers are dispersed and contained are also preferably used. .

  The shape of these fillers is not particularly limited, and may be a pulverized filler or a spherical filler obtained by ordinary pulverization. Although the particle diameter of a filler is not specifically limited, A thing of 100 micrometers or less is used suitably from the point of operativity.

  Moreover, the compounding quantity of a filler is suitably determined according to the desired viscosity, mechanical strength, etc. In particular, when the mechanical strength of the cured product of the adhesive composition is required, it is preferable to add 100 to 1200 parts by weight of the filler with respect to 100 parts by weight of the radical polymerizable monomer, and more preferably 300 to It is more preferable to add 1000 parts by weight.

  In the adhesive composition of the present invention, a polymerization inhibitor such as hydrone, hydroquinone monomethyl ether and butylhydroxytoluene, an ultraviolet absorber, a pigment, an organic solvent, a thickener, etc. It is also possible to add. Examples of the organic solvent include alcohols such as ethanol, 2-propanol, ethylene glycol, and diethylene glycol; ketones such as acetone and methyl ethyl ketone; hexane, toluene, dichloromethane, and ethyl acetate. A plurality of these organic solvents can be mixed and used as necessary.

  The adhesive composition of the present invention is used in a storage form such as a one-pack type or a one-paste type in which the above-described components are uniformly mixed in one agent. The mixing method is not particularly limited, and the above components may be mixed and stirred until uniform.

  The adhesive composition of the present invention is used as an adhesive when a ceramic dental restoration is bonded to a tooth. Here, examples of the dental restoration made of ceramic include crown restorations such as crowns, inlays, and onlays, and laminate veneers.

  As ceramics used as materials for these dental restorations, those used as porcelain and other known ceramic materials used as materials for other dental restorations can be used without limitation. As these ceramics, as is clear from the specific method for adhering the adhesive composition of the present invention described below to a dental restoration, these ceramics are exposed to light to cure the adhesive composition. Those that are excellent in transparency are preferred so that the light can easily pass through. Specific examples of such ceramics include silica-based crystallized glass, amorphous glass, and alumina-based ceramics. These materials are derived from the fact that they contain many oxygen atoms as constituent elements, and the surface of the material is covered with hydroxyl groups, forming a strong chemical bond with the silanol groups of the activated silane coupling agent. To do. Adsorption of the silane coupling agent to the hydroxyl group on the surface of the material varies depending on the constituent metal elements, etc., and ceramics containing many silicon atoms as the main constituent element, such as silica-based crystallized glass, have excellent adhesion to the coupling agent. Therefore, it is preferable.

  A method for adhering a ceramic restoration to a treatment site of a tooth using the adhesive composition of the present invention is not particularly limited, and may be performed according to a conventional method. Usually, after first applying the adhesive composition of the present invention to the restoration, it is adhered to the treatment site in the oral cavity, and then the side not applied to the application surface of the adhesive composition In general, the adhesive composition is cured by allowing the ceramics to pass through and irradiating with light.

  A known dental irradiator can be used as a means for irradiating the adhesive composition with light. Specifically, a dental irradiator using halogen, xenon, LED or the like as a light source can be exemplified. The irradiation time varies depending on the wavelength and intensity of the light source and the components of the present invention to be used, but is generally in the range of about 3 to 60 seconds.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.

Next, the abbreviations or structures of the compounds used in the examples are shown below.
(1) Abbreviation or structure (A) Radical polymerizable monomer D-2.6E: 2,2-bis (4- (methacryloyloxyethoxy) phenyl) propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl Methacrylate UDMA: Di-2- (meth) acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate MDP: 10-methacryloxydecyl dihydrodiene phosphate (B) coupling agent A-174 (trade name Nihon Unicar) Ltd.): γ-methacryloxypropyltrimethoxysilane Z-174: ω-methacryloxydecyltrimethoxysilane (C) sensitizing dye

(D) Photoacid generator, photobase generator / photoacid generator

Photobase generator PB-1: bis [[(2-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane PB-2: [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] propylamine PB-3: propionyl acetophenone oxime (E) photoradical generator, sulfinate, aryl borate compound / photo radical generator CQ: camphorquinone / photopolymerization accelerator DMBE: p-dimethylaminobenzoic acid ethyl ester / aryl borate compound PBNa: Sodium tetraphenyl boron / sulfinate PTSNa: Sodium p-toluenesulfinate (F) Filler F1: Quartz powder (non-spherical pulverized product) with an average particle size of 9 μm is surfaced with γ-methacryloyloxypropyltrimethoxysilane Treated filler 2: Filler in which spherical silica-zirconia having an average particle size of 0.2 μm is surface-treated with γ-methacryloyloxypropyltrimethoxysilane F3: 200 parts by weight of F2 is filled in a mixed solution of bis-GMA 60 parts by weight and 3G 40 parts by weight Inorganic organic composite filler having an average particle diameter of 20 μm obtained by heat polymerization using azobisisobutyronitrile as a catalyst and pulverizing the resulting cured product (2) 1 dental paste Adhesive strength to dental ceramics using mold adhesive composition “Ceraeste” (made by Tokuyama Dental Co., Ltd., 10 × 10 × 1 mm), which is a dental ceramic made of silica-based crystallized glass as an adherend ) Was used to create a test piece. This ceramic test piece was polished with # 1500 water-resistant abrasive paper, and an adhesive tape with a 3 mmφ hole was affixed to the treated surface to fix the adhesion area. The adhesive composition of Example or Comparative Example was placed on the adhesive surface, and a previously polished 8 mmφ × 18 mm round bar made of SUS304 was pressed. After the press contact, light was irradiated for 10 seconds with a visible light irradiator (white light, manufactured by Takara Belmont Co., Ltd.) so that the test piece was transmitted from the opposite side of the adhesive surface.

The test piece to which the cured product of the adhesive composition was adhered was immersed in water at 37 ° C., taken out from the water after 24 hours, and the adhesive composition was obtained using an autograph (crosshead speed 2 mm / min) manufactured by Shimadzu Corporation. The tensile bond strength of the cured product was measured. The measurement values of 6 test pieces were averaged to obtain measurement results.
Example 1
3.0 g coupling agent A-174, 0.01 g sensitizing dye CDAC, 1.0 g photoacid generator TCT, 0.25 g photoradical generator CQ, and 1 g photopolymerization accelerator DMBE, Mix with a total of 100.0 g radical polymerizable monomer consisting of 80.0 g D-2.6E, 10.0 g 3G and 10.0 g HEMA, then 200.0 g F1 and 200.0 g A total of 400.0 g of filler composed of F2 was mixed to obtain an adhesive composition. According to the test method, the adhesive strength of the adhesive composition to the ceramic test piece was examined. As a result, an adhesive strength of 18.7 MPa was exhibited for the test piece.

  Moreover, after preparing the said adhesive composition, it was preserve | saved for three months in a 37 degreeC thermostatic chamber in order to evaluate the storage stability of this adhesive composition. The adhesive composition after storage was examined for adhesion strength to a ceramic test piece in accordance with the above test method. As a result, an adhesive strength of 19.5 MPa was exhibited for the test piece.

Even when the adhesive composition stored at 37 ° C. for 3 months was used, the adhesive strength to the ceramic test piece was not significantly reduced compared to the initial value.
Example 2
3.0 g coupling agent A-174, 0.01 g sensitizing dye CDAC, 1.0 g photobase generator PB-1, 0.25 g photoradical generator CQ, and 1 g photopolymerization accelerator DMBE Is mixed with a total of 100.0 g of radically polymerizable monomer consisting of 80.0 g D-2.6E, 10.0 g 3G and 10.0 g HEMA, then 200.0 g F1 and 200. A total of 400.0 g of filler consisting of 0 g of F2 was mixed to make an adhesive composition. According to the above test method, the adhesive effect of the adhesive composition on the ceramic test piece was examined. As a result, an adhesive strength of 19.2 MPa was exhibited with respect to the test piece.

  Moreover, after preparing the said adhesive composition, it was preserve | saved for three months in a 37 degreeC thermostatic chamber in order to evaluate the storage stability of this adhesive composition. The adhesive composition after storage was examined for adhesion strength to a ceramic test piece in accordance with the above test method. As a result, an adhesive strength of 17.8 MPa was exhibited for the test piece.

Even when the adhesive composition stored at 37 ° C. for 3 months was used, the adhesive strength to the ceramic test piece was not significantly reduced compared to the initial value.
Example 3
3.0 g coupling agent A-174, 0.01 g sensitizing dye CDAC, 0.9 g photoacid generator TCT, 0.1 g photobase generator PB-1, 0.25 g photoradical generator CQ, and 0.25 g of photopolymerization accelerator DMBE, a total of 100.0 g of radically polymerizable monomer consisting of 80.0 g D-2.6E, 10.0 g 3G and 10.0 g HEMA; Next, a total of 400.0 g of filler composed of 200.0 g of F1 and 200.0 g of F2 was mixed, and this was used as an adhesive composition. According to the test method described above, the adhesive strength of the adhesive composition to the ceramic test piece was examined. As a result, an adhesive strength of 18.3 MPa was exhibited with respect to the test piece.

  Moreover, after preparing the said adhesive composition, it was preserve | saved for three months in a 37 degreeC thermostatic chamber in order to evaluate the storage stability of this adhesive composition. The adhesive composition after storage was examined for adhesion strength to a ceramic test piece in accordance with the above test method. As a result, an adhesive strength of 17.9 MPa was exhibited with respect to the test piece.

Even when the adhesive composition stored at 37 ° C. for 3 months was used, the adhesive strength to the ceramic test piece was not significantly reduced compared to the initial value.
Example 4
3.0 g coupling agent A-174, 0.01 g sensitizing dye CDAC, 1.0 g photoacid generator TCT, and 1 g arylborate compound PBNa, 80.0 g D-2.6E and 10 Mixed with a total of 100.0 g of radically polymerizable monomer consisting of 0.0 g of 3G and 10.0 g of HEMA, and then a total of 400.0 g of filler consisting of 200.0 g of F1 and 200.0 g of F2; This was mixed to obtain an adhesive composition. According to the above test method, the adhesive effect of the adhesive composition on the ceramic test piece was examined. As a result, an adhesive strength of 19.0 MPa was exhibited for the test piece.

  Moreover, after preparing the said adhesive composition, it was preserve | saved for three months in a 37 degreeC thermostatic chamber in order to evaluate the storage stability of this adhesive composition. The adhesive composition after storage was examined for adhesion strength to a ceramic test piece in accordance with the above test method. As a result, an adhesive strength of 18.8 MPa was exhibited for the test piece.

Even when the adhesive composition stored at 37 ° C. for 3 months was used, the adhesive strength to the ceramic test piece was not significantly reduced compared to the initial value.
Example 5
3.0 g coupling agent A-174, 0.01 g sensitizing dye CDAC, 1.0 g photoacid generator TCT, and 1.5 g sulfinate PTSNa, 80.0 g D-2.6E. And a total of 100.0 g of radically polymerizable monomer consisting of 10.0 g of 3G and 10.0 g of HEMA, and then a total of 400.0 g of 200.0 g of F1 and 200.0 g of F2. This was mixed with a filler to make an adhesive composition. According to the above test method, the adhesive effect of the adhesive composition on the ceramic test piece was examined. As a result, an adhesive strength of 19.5 MPa was exhibited for the test piece.

  Moreover, after preparing the said adhesive composition, it was preserve | saved for three months in a 37 degreeC thermostatic chamber in order to evaluate the storage stability of this adhesive composition. The adhesive composition after storage was examined for adhesion strength to a ceramic test piece in accordance with the above test method. As a result, an adhesive strength of 18.2 MPa was exhibited for the test piece.

Even when the adhesive composition stored at 37 ° C. for 3 months was used, the adhesive strength to the ceramic test piece was not significantly reduced compared to the initial value.
Example 6
3.0 g coupling agent A-174, 0.01 g sensitizing dye CDAC, 1.0 g photoacid generator TCT, 0.25 g photosensitizer CQ, 1 g photopolymerization accelerator DMBE, 1 g Aryl borate compound PBNa, and 1.5 g sulfinate PTSNa, a total of 100.0 g of radical polymerizable monomer consisting of 80.0 g D-2.6E, 10.0 g 3G and 10.0 g HEMA And then mixed with a total of 400.0 g filler consisting of 200.0 g F1 and 200.0 g F2 to make an adhesive composition. According to the above test method, the adhesive effect of the adhesive composition on the ceramic test piece was examined. As a result, an adhesive strength of 18.4 MPa was exhibited with respect to the test piece.

  Moreover, after preparing the said adhesive composition, it was preserve | saved for three months in a 37 degreeC thermostatic chamber in order to evaluate the storage stability of this adhesive composition. The adhesive composition after storage was examined for adhesion strength to a ceramic test piece in accordance with the above test method. As a result, an adhesive strength of 17.6 MPa was exhibited for the test piece.

Even when the adhesive composition stored at 37 ° C. for 3 months was used, the adhesive strength to the ceramic test piece was not significantly reduced compared to the initial value.
Comparative Example 1
In Example 1, the adhesive strength to the ceramic test piece was evaluated in the same manner as in Example 1 except that no coupling agent was added to the adhesive composition. As a result, the adhesive strength to the test piece was a low value of 4.2 MPa.
Comparative Example 2
In Example 1, the adhesive strength to the ceramic test piece was evaluated in the same manner as in Example 1 except that no sensitizing dye was added to the adhesive composition. As a result, when the adhesion strength to the test piece was evaluated without adding a sensitizing dye, the adhesion strength was a low value of 3.3 MPa.
Comparative Example 3
In Example 1, the adhesive strength with respect to the ceramic test piece was evaluated in the same manner as in Example 1 except that the photoacid generator was not added to the adhesive composition. As a result, when the adhesion strength to the test piece was evaluated without adding a sensitizing dye, the adhesion strength was a low value of 4.9 MPa.
Comparative Example 4
In Example 1, the adhesive strength to the ceramic test piece was evaluated in the same manner as in Example 1 except that no photoradical generator was added to the adhesive composition. As a result, when the adhesion strength to the test piece was evaluated without adding a sensitizing dye, the adhesion strength was a low value of 4.9 MPa.

Examples 7-31
The adhesive composition which consists of a composition of Table 1 was prepared, and the adhesive effect and storage stability were investigated similarly to Examples 1-6. As a result, in each of the Examples, better adhesive strength was obtained as compared with the Comparative Example, and the adhesive effect and storage stability of the adhesive composition of each Example could be confirmed.

Comparative Example 5
In the adhesive composition used in Example 1, sensitizing dye and photoacid generator were not blended, and 5 g of the radical polymerizable monomer D-2.6E used was 80 g of an acidic organic phosphorus compound. The adhesive strength to the ceramic test piece was evaluated in the same manner as in Example 1 except that the MDP was replaced. As a result, the test piece exhibited an adhesive strength of 17.5 MPa.

  Moreover, after preparing the said adhesive composition, it was preserve | saved for three months in a 37 degreeC thermostatic chamber in order to evaluate the storage stability of this adhesive composition. When the adhesive composition after storage was examined for adhesive strength to a ceramic test piece in accordance with the above test method, it had only an adhesive strength of 2.7 MPa.

Claims (3)

At least the following (A) ~ (E)
(A) a radical polymerizable monomer,
(B) Coupling agent (C) Sensitizing dye (D) Photoacid generator and / or photobase generator, and (E) Photoradical generator, or a photoacid generator as the component (D) was used. In some cases, an adhesive composition for a dental restoration made of a ceramic comprising a storage form in which each component of an aryl borate compound or a sulfinate is mixed into one agent.   Furthermore, the adhesive composition for dental restorations made of ceramics according to claim 1, further comprising (F) a filler. (B) The adhesive composition for dental restorations made of ceramics according to claim 1 or 2, wherein the coupling agent is a silane coupling agent having a polymerization group.